EP0822608B1 - Electrolyte solide polymère et pile rechargeable au lithium contenant cet électrolyte - Google Patents

Electrolyte solide polymère et pile rechargeable au lithium contenant cet électrolyte Download PDF

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EP0822608B1
EP0822608B1 EP97305697A EP97305697A EP0822608B1 EP 0822608 B1 EP0822608 B1 EP 0822608B1 EP 97305697 A EP97305697 A EP 97305697A EP 97305697 A EP97305697 A EP 97305697A EP 0822608 B1 EP0822608 B1 EP 0822608B1
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Prior art keywords
solid electrolyte
polymeric solid
solvent
electrolyte
formula
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English (en)
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EP0822608A3 (fr
EP0822608A2 (fr
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Doo-Yeon Lee
Sang-Hyun Sung
Yasumasa Hirai
Seok-Gwang Doo
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Samsung Electronics Co Ltd
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Samsung Electronics Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
    • H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
    • H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
    • H01B1/122—Ionic conductors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/14—Cells with non-aqueous electrolyte
    • H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
    • H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
    • H01M6/164—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by the solvent
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a polymeric solid electrolyte and a lithium secondary cell adopting the same, and more particularly, to a polymeric solid electrolyte having excellent ion conductivity, which can be processed easily due to its excellent mechanical property.
  • the invention further relates to a lithium secondary cell adopting such a polymeric solid electrolyte.
  • a secondary cell having high energy density, used as a driving source thereof is required.
  • secondary cells including the nickel-cadmium cell, the nickel-hydrogen cell, the lithium ion cell and so on.
  • the lithium ion cell has been the focus as a next generation power source due to its long lifetime and high capacity.
  • the Sony Energy Tech. Co. developed a lithium-carbon secondary cell having lithium anode obtained from lithium-cobalt oxide and carbon cathode.
  • the Moly Energy Co. commercialized a lithium-carbon secondary cell having lithium anode obtained from lithium nickel oxide and carbon cathode.
  • lithium cobalt oxide LiCoO 2
  • lithium nickel oxide LiNiO 2
  • lithium manganese oxide LiMn 2 O 4
  • cathode active material metallic lithium, lithium alloy or carbon is used.
  • liquid or solid electrolyte is used as an electrolyte.
  • many problems related to stability e.g., breakage of cell caused by evaporation, occur.
  • usage of a solid electrolyte instead of the liquid electrolyte has been proposed.
  • solid electrolyte does not leak electrolyte solution and is easily processed. Thus, research into the solid electrolyte has been actively performed. Interest in a polymeric solid electrolyte is particularly great.
  • the polymeric solid electrolyte is classified into a solid type without an organic electrolyte solution and a gel type including organic electrolyte solution.
  • a crosslinked polyether substance is included in the solid type.
  • the solid type electrolyte has a conductivity of about 10 -4 S/cm. However, in order to apply the electrolyte to a cell, a conductivity of 10 -3 S/cm or more is required. Thus, it is difficult in practice to use the solid type electrolyte due to its insufficient conductivity and poor mechanical property.
  • the gel type solid electrolyte is being focused as a material of the secondary cell, having high possibility to be practically used, due to its conductivity of 10 -3 S/cm or more and sufficient mechanical intensity.
  • Japanese Laid-open Patent Publication No. 4-306560 discloses a polymeric solid electrolyte including a copolymer of acrylonitrile and methyl acrylate or a copolymer of acrylonitrile and methyl methacrylate, support electrolyte salt and solvent such as propylene carbonate.
  • this kind of electrolyte has the following problems.
  • Japanese Laid-open Patent Publication No. 3-207752 discloses a polymeric solid electrolyte manufactured by irradiating ultraviolet rays onto a liquid composition including polyethylene glycol and/or dimethacrylate, support electrolyte salt and solvent.
  • the electrolyte has excellent plasticity and poor conductivity of 10 -4 S/cm or less, so that it is difficult to apply the electrolyte to a cell.
  • U.S. Patent No. 5,463,179 introduces a rigid functional group such as an alkyl group in a polymer matrix, resulting in a stable three-dimensional space within the polymer matrix.
  • a rigid functional group such as an alkyl group in a polymer matrix
  • the processing property thereof is not suitable even if the conductivity is remarkably increased.
  • a polymeric solid electrolyte which comprises a polymer matrix composed of a copolymer of polymerizable monomer represented by formula (1) and cross-linking agent represented by the formula (2).
  • R 1 is hydrogen or a methyl group
  • R 2 and R 3 are each independently selected from hydrogen, C 1 ⁇ C 6 alkyl group,-(R)N(R') 2 and -(R")OH
  • R 4 and R 5 are independently hydrogen or a methyl group
  • n is an integer of from 3 to 30, wherein R, R' and R" are C 1 ⁇ C 6 alkyl groups.
  • a lithium secondary cell adopting the polymeric solid electrolyte, providing improvement in the operating voltage, lifetime and energy density.
  • the solvent includes a non-aqueous solvent with high dielectric constant or the non-aqueous solvent (first solvent) and a second solvent having an amide group.
  • a polymeric solid electrolyte according to the present invention comprises a polymer matrix, a polymerization initiator and an electrolyte solution.
  • the polymer matrix is composed of a polymer formed by the copolymerization between a polymerizable monomer of formula (1) and a cross-linking agent of fomula (2).
  • the content of the polymerizable monomer is 10-15wt%, and the content of the cross-linking agent is 5-15wt%, based on the weight of the polymeric solid electrolyte.
  • a mixing ratio of the polymerizable monomer and the cross-linking agent is preferably 1:9 ⁇ 9:1 based on weight, which results in advantageous mechanical properties and conductivity.
  • the content of the polymerization initiator is 0.5 ⁇ 1.5wt%, and the content of the electrolyte solution is 68.5 ⁇ 84.5wt%, based on the weight of the polymeric solid electrolyte.
  • the electrolyte solution is composed of a solvent and an inorganic salt, and the content of the inorganic salt is 6 ⁇ 17wt% based on the total weight of the electrolyte solution.
  • the solvent a non-aqueous solvent is used independently, or a mixture of the non-aqueous solvent and a solvent containing an amide group is used.
  • Examples of the polymerizable monomer of formula (1) are acrylamide, N,N-dimethylacryl amide, N,N-diethylacrylamide, N-isopropylacrylamide, N,N-dimethylaminopropylacrylamide, and acryloyl morpholine. Among these, N-isopropylacryl amide and acryloyl morpholine are preferred.
  • cross-linking agent of formula (2) examples include polyethyleneglycol diacrylate and polyethyleneglycol dimethacrylate, wherein the number of the repeating unit of oxyethylene may be 1 ⁇ 30, preferably, 3 ⁇ 30.
  • n is 1 or 2
  • the plasticity slightly decreases.
  • the solvent of the electrolyte solution is a non-aqueous solvent, particulaly, capable of being dissociated due to its high dielectric constant and polarity.
  • a mixture of the non-aqueous solvent (first solvent) and a second solvent capable of being contained within a matrix due to its excellent affinity to the polymer matrix may be used.
  • the solvent is included so as to maintain the polymeric solid electrolyte in a gel state.
  • the content of the electrolyte solution includes the inorganic salt and the solvent is 68.5-84.5wt% based on the weight of the polymeric solid electrolyte.
  • the first solvent a solvent showing no phase separating phenomenon when mixed with the compound of formula (1) and (2) is preferred. Particularly, it is preferable to select one from propylene carbonate, ethylene carbonate, ⁇ -butyrolactone, 1,3-dioxolane, dimethoxyethane, dimethyl carbonate, diethyl carbonate, tetrahydrofuran (THF), dimethylsulfoxide and polyethyleneglycol dimethylether.
  • the second solvent a solvent having an amide group as in the polymerizable monomer of formula (1) is used.
  • the second solvent includes N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide and N,N-diethylformamide.
  • the electrolyte solution is evenly distributed within the network structure of the polymer matrix and viscosity of the electrolyte solution is lowered, improving the ion conductivity of a support electrolyte salt being dissolved within the solvent.
  • a mixing ratio of the first solvent and the second solvent is 1:3-3:1 based on volume, more preferably, 1:1 based on volume. If the mixing ratio of the second solvent with respect to the first solvent is above this range, the mechanical strength of the electrolyte is markedly decreased, so that the electrolyte is fragile during the cell assembly. Meanwhile, if the mixing ratio thereof is below the range, the ion conductivity of the electrolyte decreases and the electrolyte hardens.
  • an ionic lithium salt is selected from lithium perchlorate (LiClO 4 ), lithium tetrafluoroborate (LiBF 4 ), lithium hexafluorophosphate (LiPF 6 ), lithium trifluoromethansulfonate (LiCF 3 SO 3 ) and lithium bistrifluoromethansulfonylamide (LiN(CF 3 SO 2 ) 2 ).
  • the content of the ionic inorganic salt is 6 ⁇ 17wt.% based on the weight of the electrolyte solution.
  • the contentration of the ionic inorganic salt with respect to the solvent is 0.5 ⁇ 1.5M.
  • the concentration of the ionic inorganic salt exceeds 1.5M, mobility of the lithium ions is decreased and the ion conductivity is sharply decreased.
  • the concentration of the ionic inorganic salt is less than 0.5M, the number of ions participating in the movement of the lithium ions is decreased, thereby decreasing the ion conductivity.
  • the polymeric solid electrolyte according to the present invention is obtained through the following steps.
  • a polymerizable monomer having an amide group as a side chain, and polyethyleneglycol diacrylate or dimethacrylate are mixed with a weight ratio of 1:9 ⁇ 9:1, and then an ionic inorganic salt and a solvent are added to the mixture to produce a polymeric solid electrolyte composition.
  • the polymeric electrolyte composition is coated on a support such as aluminum thin film and mylar film using a doctor blade or a bar coater, and then polymerization is performed to complete a polymeric solid electrolyte according to the present invention.
  • the polymerization initiator includes a photopolymerization or thermalpolymerization initiator.
  • a photopolymerization initiator there are 2-hydroxy-2-methyl-1-phenylpropane, 1-hydroxycyclohexylphenylketone, 1-(4-isoprophlphenyl)-2-hydroxy-2-methylpropane), benzyldimethylketal, benzoin, benzoinethylether.
  • the thermalpolymerization initiator there are azobisisobutyronitrile and benzoyl peroxide.
  • one active material for the lithium cathode selected from lithium manganese oxide, lithium nickel oxide and lithium cobalt oxide, and a conductive agent are added to the composition for the polymeric solid electrolyte including the polymerizable monomer of the formula (1), the cross-linking agent of the formula (2), the polymerization initiator, the electrolyte solution containing the inorganic salt and the solvent, and then mixed well to form a reaction mixture.
  • the heating is performed to form a composite cathode layer.
  • a mixture of carbon powder and the composition for the polymeric solid electrolyte is coated on a anode current collector and then heated to form a composite anode layer.
  • the overlapped layers are combined by a thermal process or applying a predetermined pressure, thereby completing a lithium secondary cell of the present invention.
  • N-isopropylacryl amide and polyethyleneglycol dimethacrylate were mixed with a weight ratio of 3:1, and then propylene carbonate including 1M LiBF 4 and benzoinethylether were added to the mixture, resulting in a polymeric electrolyte composition.
  • propylene carbonate including 1M LiBF 4 and benzoinethylether were added to the mixture, resulting in a polymeric electrolyte composition.
  • the substrate was subjected to ultraviolet rays for 30 minutes to obtain a gel type polymeric solid electrolyte.
  • a gel type polymeric solid electrolyte was obtained by the same method as that of Example 1, except N-acryloyl morpholine was used instead of N-isopropylacryl amide.
  • a gel type polymeric solid electrolyte was obtained by the same method as that of Example 1, except ⁇ -butyrolactone was used instead of propylene carbonate.
  • Ethylene carbonate containing 1M LiPF 6 and N,N-dimethylacetamide were mixed with 1:1 volumetric ratio to prepare an electrolyte solution.
  • N-isopropylacrylamide and polyethyleneglycol dimethacrylate were added to the electrolyte solution with a weight ratio of 3:1, and then benzoylethylether was mixed thereinto.
  • the above composition was coated on a glass substrate and then the resultant was subjected to ultraviolet rays for about 30 minutes to be polymerized, resulting in a gel type polymeric solid electrolyte.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except N,N-dimethylformamide was used instead of N, N-dimethylacetamide.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except N,N-diethylacetamide was used instead of N, N-dimethylacetamide.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except N,N-diethylformamide was used instead of N, N-dimethylacetamide.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except the concentration of LiPF 6 was 0.5M.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except the concentration of LiPF 6 was 1.0M.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except the concentration of LiPF 6 was 1.5M.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except ethylene carbonate and N,N-dimethylacetamide were mixed with a volumetric ratio of 1:3.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except ethylene carbonate and N,N-dimethylacetamide was mixed with a volumetric ratio of 3:1.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except propylene carbonate was used instead of ethylene carbonate.
  • a gel type polymeric solid electrolyte was produced by the same method as that of Example 4 except 1M LiBF 4 was used instead of 1M LiPF 6 .
  • a gel type film having a diameter of 13mm was prepared from respective polymeric solid electrolytes obtained through Examples 1 to 14. After putting the film between two stainless steel disks, the ion conductivities were measured using an impedance analyzer adopting an alternating current impedance method.
  • a gel type film was wound around a stainless steel rod having a diameter of 5mm. Then, the film was unwound from the rod. This process was repeated about 10 times, and then the appearance of the film was visually checked.
  • the visual appearance of the film was evaluated into one of three levels: excellent, good or poor, wherein “excellent” represents a state in which no defects are visually detected in the gel type film, "good” represents a state in which very trivial defects are detected, which would not have an adverse effect in usage, and "poor” represents a state in which defects are visually detected.
  • a filter paper was attached to the gel type film for a predetermined time. Then, it was observed whether the electrolyte solution leaks or not.
  • Example 1 As shown in Table 1, the ion conductivities of the polymeric solid electrolyte according to Examples 1-14 were improved. Also, flexibility of the electrolytes manufactured in Examples 1-11 and 13-14 was good. However, in the case of Example 12, the flexibility of the electrolyte was decreased due to the formation of a hard polymer gel.
  • the polymeric solid electrolyte according to the present invention provides the following effects: 1) the organic electrolyte solution hardly leaks from the electrolyte; 2) the electrolyte can be easily processed due to its excellent mechanical properties such as flexibility and plasticity; 3) the electrolyte can be applied to a lithium secondary cell requiring excellent ion conductivity due to its high conductivity of 10 -3 S/cm or more.

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Claims (17)

  1. Electrolyte solide polymère comprenant une matrice polymère composée d'un copolymère de monomère polymérisable représenté par la formule (1) et d'un agent de réticulation représenté par la formule (2).
    un amorceur de polymérisation:
    une solution d'électrolyte contenant un sel inorganique et un solvant:
    Figure 00250001
    Figure 00250002
    dans lesquelles R1 est un atome d'hydrogène ou un groupe méthyle, et R2 et R3 sont, indépendamment l'un de l'autre, choisis parmi un atome d'hydrogène, un groupe alkyle en C1 à C6, -(R)N(R')2 et -(R'')OH, et R4 et R5 sont, indépendamment l'un de l'autre, un atome d'hydrogène ou un groupe méthyle, n est un nombre entier de 3 à 30, dans lequel R, R' et R'' sont des groupes alkyle en C1 à C6.
  2. Electrolyte solide polymère selon la revendication 1, dans lequel un rapport de mélange du monomère polymérisable représenté par la formule (1) et d'un agent de réticulation représenté par la formule (2) est de 1:9 à 9:1 en poids.
  3. Electrolyte solide polymère selon la revendication 1 ou 2, dans lequel le monomère polymérisable représenté par la formule (1) est au moins un monomère choisi parmi l'acrylamide, le N,N-diméthylacrylamide, le N,N-diéthylacrylamide, le N-isopropylacrylamide, le N,N-diméthylaminopropylacrylamide et l'acryloylmorpholine.
  4. Electrolyte solide polymère selon- l'une quelconque des revendications 1 à 3, dans lequel l'agent de réticulation est le diacrylate de polyéthylèneglycol ou le diméthacrylate de polyéthylèneglycol.
  5. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 4, dans lequel le solvant est un solvant non aqueux.
  6. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 4, dans lequel le solvant est un mélange de solvant non aqueux et d'un solvant ayant un groupe amide.
  7. Electrolyte solide polymère selon la revendication 5 ou 6, dans lequel le solvant non aqueux est au moins un solvant choisi parmi le carbonate de propylène, le carbonate d'éthylène, la γ-butyrolacétone, le 1,3-dioxolane, le diméthoxyéthane, le carbonate de diméthyle, le carbonate de diéthyle, le tétrahydrofuranne (THF), le diméthysulfoxyde et l'éther diméthylique de polyéthylèneglycol.
  8. Electrolyte solide polymère selon la revendication 6, dans lequel le solvant ayant le groupe amide est au moins un solvant choisi parmi le N,N-diméthylacétamide, le N,N-diéthylacétamide, le N,N-diméthylformamide et le N,N-diéthylformamide.
  9. Electrolyte solide polymère selon l'une quelconque des revendications 6 à 8, dans lequel le rapport de mélange du solvant non aqueux et du solvant ayant le groupe amide est de 1:3 à 3:1 en volume.
  10. Electrolyte solide polymère selon la revendication 9, dans lequel le rapport de mélange du solvant non aqueux et du solvant ayant le groupe amide est de 1:1 en volume.
  11. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 10, dans lequel le sel inorganique est au moins un sel choisi parmi le perchlorate de lithium (LiClO4), le tétrafluoroborate de lithium (LiBF4), l'hexafluorophosphate de lithium (LiPF6), le trifluorométhanesulfonate de lithium (LiCF3SO3) et le bistrifluorométhanesulfonylamide de lithium (LiN(CF3SO2)2.
  12. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 11, dans lequel la teneur en monomère polymérisable représenté par la formule (1) est de 10 à 15% par rapport au poids de l'électrolyte solide polymère.
  13. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 12, dans lequel la teneur en agent de réticulation représenté par la formule (2) est de 5 à 15% en poids par rapport au poids de l'électrolyte solide polymère.
  14. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 13, dans lequel la teneur de l'amorceur de polymérisation est de 0,5 à 1,5% en poids par rapport au poids de l'électrolyte solide polymère.
  15. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 14, dans lequel la teneur de la solution d'électrolyte est de 68,5 à 84,5% en poids par rapport au poids de l'électrolyte solide polymère.
  16. Electrolyte solide polymère selon l'une quelconque des revendications 1 à 15, dans lequel la teneur en sel inorganique retenu par le polymère de monomère de formule (1) est de 6 à 17% en poids par rapport au poids de la solution d'électrolyte.
  17. Accumulateur au lithium contenant l'électrolyte solide polymère selon l'une quelconque des revendications 1 à 16.
EP97305697A 1996-07-30 1997-07-29 Electrolyte solide polymère et pile rechargeable au lithium contenant cet électrolyte Expired - Lifetime EP0822608B1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR9631528 1996-07-30
KR19960031528 1996-07-30
KR1019960046314A KR19980027516A (ko) 1996-10-16 1996-10-16 고분자 고체 전해질 및 이를 채용한 리튬 2차전지
KR9646314 1996-10-16
KR1019970030817A KR100261252B1 (ko) 1996-07-30 1997-07-03 고분자 고체 전해질 및 이를 채용하고 있는 리튬 2차전지
KR9730817 1997-07-03

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EP0822608A2 EP0822608A2 (fr) 1998-02-04
EP0822608A3 EP0822608A3 (fr) 1999-08-04
EP0822608B1 true EP0822608B1 (fr) 2001-11-28

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US (1) US5952126A (fr)
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JP (1) JPH10116516A (fr)
KR (1) KR100261252B1 (fr)
DE (1) DE69708547T2 (fr)

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KR980012680A (ko) 1998-04-30
US5952126A (en) 1999-09-14
EP0822608A3 (fr) 1999-08-04
EP0822608A2 (fr) 1998-02-04
DE69708547T2 (de) 2002-05-08
KR100261252B1 (ko) 2000-07-01
DE69708547D1 (de) 2002-01-10

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